Catalytic converter



Oct. 4, 1949. E, KLEIBER ETAL 2,483,494

CATALYTIC CONVERTER 2 She ets-Sheet 2 Original Filed May 12, 1943 19 STEAM 21 //VLET .22 l 55 25 Patented Oct. 4, 1949 NITED STATES PATENT FlFl-CE '2;483,494 oa'railrric CONVERTER :(Jarl E. 'Kleiber, 'Irv'ington, Donald L. Campbell, Short Hills, Daniel E. Stines, Plainfield, and

Charming C. Nelson, Cranford, N. J., assignors to 'StandardtOiI Development Company, a corporation of Delaware Original application May 12. 1943, S a ;;No-

486,636. Divided'a-nd this application April 'l, 1-945, Serial No. 587,170

7 .2 Claims. (01. 23-288) This invention :relates to equipment for the catalytic dehydrogenation of normally gaseous hydrocarbons in a continuous operation under closely -=controlled conditions of time; tempera- *ture and pressure whereby improved results are achieved. In particular, the present invention relates to equipment for the dehydrogenation of olefins such as normal butenes (thexword butenes" when used hereinafter refers to normal =butenes) to form diolefins-such -as butadiene or for' the dehydrogenation of alkylated-aromatic such-as ethyl benzene to form styrene.

This application is a division of application Ser'ia'PNo. 486,636, filed May 12, 1-943,-noW Patent No. 211143316.

The dehydrogenation of -butenes to form 'bu- "tadien'e is a reaction which is preferably conducted at;relative ly' low partial pressures. Thus "butenes inthe presence of a suitable catalyst may be dehydrogenated to 'form butadiene, but .ordinarily the partial pressure should be relatively low in-the-reaction'zone, and the conta'ct'time or the residence of "the reactants shouldbe suffl+ cently short, preferablyless than 2 seconds, to prevent the. occurrence of undesired side reactions and consequent loss in yield of the des red ibutadiene. Also, the length of time jthereactants are held at relatively high temperature before contact with the catalyst and thatthe products of reaction "are held atrelatively. high temperature after contact with the catalyst should be minimized for similar reasons;

'One object of our present invention is to pro- ..vide an apparatus in which the dehydrogenation can \be reflected of .butenes to butadiene in the presence of a catalyst under conditions which afiord maximumyield of butadiene fromia. given quantity of butenes ,charg-ing stock, .consistent .witha high rate of production of butadiene fora g en investment in manufacturin equi m nt.

A.mor.e specific obiectof our invention ,is to provide means ,for preheating the -,loutene'si to reaction temperatures which will permit closely controlling the reaction time and the time the reactants and produc are maintained a hi h tempe a u and thus obviate h t de y t .ward und s r d s de reacti s and de mpos tionjo'f thebutajdiene formed.

Astillfurther object of our inventionjs tolprovi'de means .for rapidly heatin the feed stools, 'suc'h-as'hutenes, to reactiontemperatures, rapidly forcing the said feed stock through a bed of catalyst, promptly withdrawing "the reaction products from contact with :the catalyst and 'guenching "the reaction products below temperatures which cause degradation .of the desired diolef1ns. A further object of ourinventiontis .tofurnish aanapparatussin Whichbutenes may be preheated,

dehydrogenated, quenched .and :butadiene recoil:-

:ered therefrom, in substantial yields, the appar- -tenes to butadiene :may be effected :under :low

partial pressure conditions to prevent .undesired side reactions.

Gther and furtherobjects of our invention will appear from "the following more detailed-descripe tion and claims.

To the accomplishment of the foregoing and related ends, in-general, weprovidea plant layout adopted to carry out the following process-z H 0 superheat steam to a temperature above the dehydrogenation reaction temperature and then discharge it into a mixing zone where it intermixes with butenes, the hutenes beingpreviously heated to a temperature somewhat below their active reaction temperature. The Icputenes are heated to reaction temperature by mixing with the superheated steam. Thereafter, the mixture then contacts a suitable catalyst. The reaction products are withdrawn fromthe reaction i zone, promptly quenched to atemperaturegbelow those at which undesirable side reactions take place, and s a e h rea ti n r du t ar .i l i a d. s v e t c d. d otherwis t eated to recover the desired butadiene.

-H v g s th the obiee of o inventiqn and a general statement otiour invention ,.,wen 0w ei o th a c m an ng-draw ng fo .aetts understanding of our invention. In describing h d ta l of thcdrawing, w lshal illu at its us in u ane d hydr en t on lnIia I .we ha u t e di rammati all 2.113129 18 8 in which a preferred mod ation of our invention may be carried-into practical e fec i .E e- I Weh ve sh wn a p ef rred fo m of reactor in vertical section; in Fig. III we have s own ap a hse tio ta e al ne main of Fis- II ofnu reacto part y brok n .t sh w the internal construction; in Big. we have show a second pl n e ti n o th r acto talien along IV-IV of Fig. II.

Referring :in detail .to Figs. I to 1 V, iblllifilifis are introduced into the system 'through line i and hence passed throu h a g ii nac .3 Wh re the are heated to a temperature of from 1000 to aisnei 1250 F. or thereabouts, thence withdrawn at this temperature through line and discharged into the top of reactor 2| (see in particular Fig. II), the preheated olefin entering through a nozzle I5, an inner projection H within the reactor shell extending into a ring manifold l8 disposed laterally in an upper portion of said reactor. As shown, particularly in Fig. II, reactor 2| is of the drum type, preferably insulated.

The rate of flow of fuel (preferably a. gas or liquid) burned in the furnace 3' is automatical y regulated by the temperature of the butenes stream at or near the outlet of the furnace. This regulator means, indicated by 4 on Fi I may be an conventional device disposed in communication with line 5 and fiow control valve 8 in fuel feed lin 9 whereby the rate of flow of fuel to furnace 3 is responsive to the temperature at or near the outlet of the butene from said furnace. In respect of the steam, the latter from some source is introduced through line l0 (see Fig. I), then passes through a superheater l2, and thence passes through pipe I4 into the ring manifold inreactor 2 l; Acontrol 90 is utilized in the steam superheater furnace hereinbelow described to control the rate of flow of fuel entering superheater l2 through the line H. It will be noted that the circular butene manifold l8 carries a plurality of taps or draw-off pipes H! which terminate at their lower ends in mixing means 22 disposed in a series of vertical pipes 24. The vertical pipes 24 are in communication with the said ring manifold 30 containing, as indicated, superheated steam. The upper ends of said pipes 24 project into manifold 30, substantially above the lower surface of said manifold so that the steam passing through the manifold tends to deposit any solid particles such as scale which it may contain and these particles are prevented from passing into the mixing means 22 and/or into the catalyst bed 25. Similar means (not shown) may be provided at the points where the butenes leave manifold |8 through lines Hi. The superheated steam, which is at a temperature of about 1400?? passes from. the manifold 30 through the pipes 24 into mixing means 22. Preferably the mixing means 22 are Venturi tubes their lower extremities projecting to points in close proximity to the bed of catalyst, and their functions 'are to cause immediate mixing of butene and superheated steam flowing therethrough with a consequent rise of the temperature of the butene to reaction inlet temperatures, namely, about 1200" F. to 1300" F., and to cause the mixture to flow into the said bed of catalyst. Since a Venturi tube is well known structure it need not be illustrated in detail. Other suitable mixing means may be employed for mixin the steam and butenes.

The process is so operated preferably, that for each volume of butene, 8-10 volumes of superheated steam are discharged into the Venturi tubes. The mixture of steam and butene, as indicated, passes into the annular bed of catalyst 25. This bed of catalyst preferably is 1 ft. 6 inches to 6 ft. thick and is manually placed in the reactor in a relatively loosely packed form with a levelled upper surface. The catalyst bed 25 in the modification shown is annularly disposed around a central cylindrical open space so that the reactants may be uniformly distributed to the upper surface of the catalyst bed 25, also, as an aid in filling the bed space with catalyst and removing the spent catalyst when desired. The

0 results.

4 number of pipes 24 discharging steam and butene into the bed of catalyst may vary. We have shown ten, but more or less may be employed. In order to prevent the gaseous mixture from flowing upwardly into the space above the catalyst bed 25 or in any direction except downwardly through the bed of catalyst 25, we provide hooded metallic members 33 about the lower extremities of mixing nozzles 22 and in contacting relation with a screen member 34 resting on the upper surface of the bed of catalyst 25. The lower portion of the mixing nozzles is cylindrical in shape and is machined to provide close clearance within the sleeves 35 of the above-mentioned hooded members 33 which sleeves are adapted for vertical adjustment. Thus, these members 33 rest upon the screen member 34, which in turn is supported by the catalyst bed 25 and although the mixing means 22 may move relative to the catalyst bed 25 the flow between the mixing means and the catalyst bed is maintained confined. Steam may be continuously bled through line 9| into the upper part of the reaction chamber 2| under a sufficient pressure to cause it to pass continually into the catalyst bed 25 through any small openings available. These openings may include the small spaces between the hooded members 33 and the mixin nozzles 22 and between the edge of the hooded members 33 and the screen member 34 and between the screen member 34 and the inside wall of the reaction chamber 2|. This flow of steam tends to prevent butenes from entering the upper part of the reaction chamber 2| above the catalyst bed 25 and there being converted by side reactions into undesirable products. The catalyst itself is preferably a catalyst consisting essentiall of iron oxide, magnesium oxide, copper oxide and potassium oxide. A preferred composition consists essentially of the following in weight per cent MgO, 72.4; FezOa, 18.4; CuO, 4.6; K20, 4.6. Other proportions may be used, e. g., the MgO may vary from -95%, the FezOa from 3 to 49%, the CuO from 0.5 to 10%, and the K20 from 0.5 to 10%. This catalyst has the advantage of being resistant to injury by contact with steam and hence is quite superior to other catalysts such as molybdenum oxide or chromium oxide supported on activated alumina which are deactivated by contact with steam. The catalyst itself is preferably in the form of extruded lengths havinga diameter of t; inch and a length of & inch, although it may alternatively be in the form of granules, lumps, shaped bodies. etc.

The velocity of the mixture of steam and butene through the catalyst bed is such that the contact time between the reactants and catalyst is of the order of one-half second, although contact times of from 0.05 to 2 seconds give good We prefer to operate under conditions such that the partial pressure of the butene as it enters the bed of catalyst is from 25 to 200 millimeters mercury absolute pressure. The reaction products are withdrawn through a foraminous member 48 which also serves as a support for the bed of catalyst, are sprayed with water at atmospheric temperature or thereabouts, sprayed or injected through pipes I00 into the reactor below the bed of catalyst 25 in order to cool the products rapidly to 900 to 1000 carrying slots I04 permitting ingress of gas or tapersinto the ring, serves as a-support' for the catalyst bed 25. I'he gaseous products pass from 25 uniformly from its lower surface and of course those which are withdrawn outside ring F823 pass into the rings through ports ltd, whence the said products pass into pipe. whose upper end projects-into the said ring;

Referring again to Fig. I, the gaseous mixture in line 42 isdischarged through a waste heat boiler where itstemperature is further reduced, say to around 500-600 F. The gaseous mixture is withdrawn through line 48 from waste heat boiler 45 and is further cooled by the addition of cool quench oilthrough line 49. The gaseous mixture then passes from valved line-48 into a quenching tower 50, where it. flows upwardly against dowrrflowing oil introduced into the tops .of the tower 58 through inlet pipe 54. The quenching oil is preferably at a temperature of 150-250" F., and this oil serves to further cool the vapors to a temperature of 300 F. The gaseous mixture is withdrawn through line 56 and discharged into a cooling and partial condensing zone 59 where it is further cooled to a temperature of 185 F., thence withdrawn through line 68 and delivered to a separating drum 62. A liquid product is withdrawn from separation drum 62 through bottom draw-oil pipe 65, while the butadiene-containing gases are withdrawn overhead through line 68 and delivered to a second quenching tower where they are quenched with water at atmospheric temperature discharged into said quenching tower through a pipe 18. The gases now cooled to approximately atmospheric temperature are withdrawn from quenching tower 15 through line 80 and then are delivered to compressing system 82 where they are partially liquefied and thence delivered to conventional fractionation, butadiene extraction, and purification equipment (not shown) by way of valved line 85. Water is withdrawn from tower 75 through line 16.

While we have shown one reactor in the drawing, we prefer to use several reactors. This is principally for reason that the use of catalyst to promote the reaction causes deposition of carbonaceous material upon the catalyst so that eventually the activity of the catalyst is reduced to the point where it becomes necessary to regenerate the catalyst by removing the carbonaceous material. The use of two or more reaction chambers permits regenerating the catalyst bed in one chamber while the other catalyst bed or beds is in use in promoting the reaction. Thus, the stream of reactants may be kept flowing continuously being transferred from one or more reactors to the same number of other reactors whenever it is desired to regenerate a catalyst bed.

During the regeneration of the catalyst in reactor 2|, we direct the flow of a portion of the steam from line It through a branch line l5, by-passing the superheater I2 so as to discharge steam into the reactor at a temperature of 1100- 1300 F. The steam converts the carbonaceous material fouling the catalyst according to the water gas reaction into H2, CO and CO2 and these gaseous materials may be withdrawn from the system through lines 42 and 43. Preferably this hot gas is passed through waste heat boiler 45 or the like to recover at least a portion of its sensible heat.

Referring to the quenching tower 50, the quenching oil which is withdrawn from the hottom through line 59 is; pumped; by pump: it through a cooler 63 bywayofeline-L Mi anda thence recycled to. inlet pipe 5'4.v A portion of the oil from tower 50 is continuously withdrawn through line 65,. discharged intoa stripper 6! from which it is withdrawn for rejection. Fresh oil is added through line F01. The purpose ofstripper this to. remove butad-iene and butenes from the oil which is: to be withdrawn from the system through line 96-for disposal. The: said buta'di'ene and butenes are returned totower '50 through line To in vapor form. 1

hereinbeiore mentioned, the temperature of the butenes entering the reaction chamber 2f through line- 5 may be' controlled' automatically as may also be-thetemperature of the-super heated steam-entering the reaction chamber 21 through line H 4. Since the. rates of flow of both streams may also be controlled, the temperature of the mixed butenes and steam entering the catalyst bed may be thus indirectly controlled. Let us suppose that an inlet temperature for the mixture of 1200 F. is the most desirable for a catalyst, freshly made. Then, after a considerable period of time during which this catalyst ages because it has been subjected to periods in which it has been used to promote reaction and between periods regenerated, it is necessary and desirable to increase the temperature of the mixture entering the catalyst because of lowered activity of the aged catalyst. This may preferably be accomplished by increasing the temperature of the stream of butenes flowing through line 5 or of the stream of steam flowing through line I4 or both, rather than by changing the rates of flow of either steam or butenes and thus reducing throughput or capacity.

The time of contact of the mixture of steam and butenes with the catalyst may be varied by shutting down the apparatus and changing the amount of catalyst in the bed 25. For convenience, pipes l9 and 24 are provided with spool pieces to permit maintaining contact between the hooded members 33 and the bed 25, whether the said bed is relatively thick or thin.

It is customary practice in most hydrocarbon processing units to start them by first purging the unit of air with steam and then passing hydrocarbon through the unit. This avoids fires and explosions. However, this practice is not suitable in starting a unit of the type described, because if equipment at substantially atmospheric temperature and containing catalyst were exposed to a current of steam, a portion of the steam would give up suflicient heat to the bed and the metal portions of the reaction chamber to cause condensation and the water thus formed would damage the catalyst. Therefore, means must be provided to free the apparatus of air in a different manner. We prefer, in initiating operations to pass air through a heat exchanger or furnace and thence through the catalyst bed until the temperature of the latter is raised to a point just above where such steam condensation would occur. The air supply is discontinued and superheated steam is passed. The apparatus required for heating the catalyst with air is not separately shown, but use may be made of a portion of the compression equipment shown, for compressing air, and of the furnaces normally used for heating normal butenes and steam.

What is claimed is:

1. A reactor for carrying out high temperature short time catalytic reactions, which comprises a vertical cylindrical reactor shell, a horizontal catalyst bed dividing the shell into upper and lower portions, distributing pipes in the upper portion of the shell for separate reactant vapors, mixing means for admixing said vapors conveyed separately thereto from the distributing pipes, a vertically disposed nozzle associated with said mixing means for discharging the mixed vapors in a confined stream downwardly toward an upper surface of the catalyst bed spaced below the lower extremity of the nozzle, and a hood member about the lower portion of the nozzle with a clearance therefrom for vertical adjustment of said hood member by independent motion with respect to the nozzle, said hood member being supported in position by contacting relationship with the catalyst bed whereby the mixed vapors are discharged from the nozzle flow in a confined stream directly into the upper surface of the catalyst bed.

REFERENCES CITED The following references are of record in the file of this patent: V

UNITED STATES PATENTS Number Name Date 2,399,560 Murphree Apr. 30, 1946 

